Thiophene and selenophene copolymers incorporating fluorinated phenylene units in the main chain: Synthesis, characterization, and application in organic field-effect transistors

D.J. Crouch, P.J. Skabara, J.E. Lohr, J.J.W. McDouall, M. Heeney, I. McCulloch, D. Sparrowe, M. Shkunov, S.J. Coles, P.N. Horton, M.B. Hursthouse

Research output: Contribution to journalArticle

137 Citations (Scopus)

Abstract

A series of thiophene oligomers bearing core phenylene and fluorinated phenylene units has been synthesized as potential semiconductor materials for organic field-effect transistors (OFETs). Polymerization of these compounds has been achieved using Stille and oxidative Coupling methods. Functionalization of the phenylene unit with fluorine atoms has a marked effect on the self-assembly and electronic properties of the parent materials: the optical band gaps and highest occupied molecular orbital levels are affected with the introduction Of fluorine atoms as a result of a combination of inductive effects and rigidification of the main chain. The design of these materials has focused on the self-assembly and solution processability of the materials. All the polymers are readily Soluble in common organic solvents. Self-assembly and planarization of the fluorinated materials in the solid state are identified by a combination of X-ray diffraction studies, absorption spectroscopy, and cyclic voltammetry. The organizational behavior of the films is in contrast to the conformational freedom observed in solution (absorption spectroscopy) and in the gas phase (computational Studies). Thin-film OFETs have been fabricated for the entire polymer series. Hole mobilities have been measured Lip to 10(-3) cm(2)/(V(.)s), with high current modulation (on/off ratios up to 10(5)) and low turn-on voltages (down to 2 V). For the Stille Coupled polymers, replacement of the bridging thiophene unit with selenophene generally increases the hole mobility of the polymers.
LanguageEnglish
Pages6567-6578
Number of pages11
JournalChemistry of Materials
Volume17
Issue number26
DOIs
Publication statusPublished - 27 Dec 2005

Fingerprint

Organic field effect transistors
Thiophenes
Thiophene
Polymers
Copolymers
Self assembly
Hole mobility
Fluorine
Absorption spectroscopy
Bearings (structural)
Atoms
Optical band gaps
Molecular orbitals
Oligomers
Electronic properties
Organic solvents
Cyclic voltammetry
Gases
Polymerization
Modulation

Keywords

  • thin-film transistors
  • conjugated polymers
  • phase-behaviour
  • solar-cells
  • semiconductors
  • derivatives
  • stacking
  • devices
  • sensors
  • oligothiophene

Cite this

Crouch, D.J. ; Skabara, P.J. ; Lohr, J.E. ; McDouall, J.J.W. ; Heeney, M. ; McCulloch, I. ; Sparrowe, D. ; Shkunov, M. ; Coles, S.J. ; Horton, P.N. ; Hursthouse, M.B. / Thiophene and selenophene copolymers incorporating fluorinated phenylene units in the main chain: Synthesis, characterization, and application in organic field-effect transistors. In: Chemistry of Materials. 2005 ; Vol. 17, No. 26. pp. 6567-6578.
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abstract = "A series of thiophene oligomers bearing core phenylene and fluorinated phenylene units has been synthesized as potential semiconductor materials for organic field-effect transistors (OFETs). Polymerization of these compounds has been achieved using Stille and oxidative Coupling methods. Functionalization of the phenylene unit with fluorine atoms has a marked effect on the self-assembly and electronic properties of the parent materials: the optical band gaps and highest occupied molecular orbital levels are affected with the introduction Of fluorine atoms as a result of a combination of inductive effects and rigidification of the main chain. The design of these materials has focused on the self-assembly and solution processability of the materials. All the polymers are readily Soluble in common organic solvents. Self-assembly and planarization of the fluorinated materials in the solid state are identified by a combination of X-ray diffraction studies, absorption spectroscopy, and cyclic voltammetry. The organizational behavior of the films is in contrast to the conformational freedom observed in solution (absorption spectroscopy) and in the gas phase (computational Studies). Thin-film OFETs have been fabricated for the entire polymer series. Hole mobilities have been measured Lip to 10(-3) cm(2)/(V(.)s), with high current modulation (on/off ratios up to 10(5)) and low turn-on voltages (down to 2 V). For the Stille Coupled polymers, replacement of the bridging thiophene unit with selenophene generally increases the hole mobility of the polymers.",
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author = "D.J. Crouch and P.J. Skabara and J.E. Lohr and J.J.W. McDouall and M. Heeney and I. McCulloch and D. Sparrowe and M. Shkunov and S.J. Coles and P.N. Horton and M.B. Hursthouse",
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Crouch, DJ, Skabara, PJ, Lohr, JE, McDouall, JJW, Heeney, M, McCulloch, I, Sparrowe, D, Shkunov, M, Coles, SJ, Horton, PN & Hursthouse, MB 2005, 'Thiophene and selenophene copolymers incorporating fluorinated phenylene units in the main chain: Synthesis, characterization, and application in organic field-effect transistors' Chemistry of Materials, vol. 17, no. 26, pp. 6567-6578. https://doi.org/10.1021/cm051563i

Thiophene and selenophene copolymers incorporating fluorinated phenylene units in the main chain: Synthesis, characterization, and application in organic field-effect transistors. / Crouch, D.J.; Skabara, P.J.; Lohr, J.E.; McDouall, J.J.W.; Heeney, M.; McCulloch, I.; Sparrowe, D.; Shkunov, M.; Coles, S.J.; Horton, P.N.; Hursthouse, M.B.

In: Chemistry of Materials, Vol. 17, No. 26, 27.12.2005, p. 6567-6578.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Thiophene and selenophene copolymers incorporating fluorinated phenylene units in the main chain: Synthesis, characterization, and application in organic field-effect transistors

AU - Crouch, D.J.

AU - Skabara, P.J.

AU - Lohr, J.E.

AU - McDouall, J.J.W.

AU - Heeney, M.

AU - McCulloch, I.

AU - Sparrowe, D.

AU - Shkunov, M.

AU - Coles, S.J.

AU - Horton, P.N.

AU - Hursthouse, M.B.

PY - 2005/12/27

Y1 - 2005/12/27

N2 - A series of thiophene oligomers bearing core phenylene and fluorinated phenylene units has been synthesized as potential semiconductor materials for organic field-effect transistors (OFETs). Polymerization of these compounds has been achieved using Stille and oxidative Coupling methods. Functionalization of the phenylene unit with fluorine atoms has a marked effect on the self-assembly and electronic properties of the parent materials: the optical band gaps and highest occupied molecular orbital levels are affected with the introduction Of fluorine atoms as a result of a combination of inductive effects and rigidification of the main chain. The design of these materials has focused on the self-assembly and solution processability of the materials. All the polymers are readily Soluble in common organic solvents. Self-assembly and planarization of the fluorinated materials in the solid state are identified by a combination of X-ray diffraction studies, absorption spectroscopy, and cyclic voltammetry. The organizational behavior of the films is in contrast to the conformational freedom observed in solution (absorption spectroscopy) and in the gas phase (computational Studies). Thin-film OFETs have been fabricated for the entire polymer series. Hole mobilities have been measured Lip to 10(-3) cm(2)/(V(.)s), with high current modulation (on/off ratios up to 10(5)) and low turn-on voltages (down to 2 V). For the Stille Coupled polymers, replacement of the bridging thiophene unit with selenophene generally increases the hole mobility of the polymers.

AB - A series of thiophene oligomers bearing core phenylene and fluorinated phenylene units has been synthesized as potential semiconductor materials for organic field-effect transistors (OFETs). Polymerization of these compounds has been achieved using Stille and oxidative Coupling methods. Functionalization of the phenylene unit with fluorine atoms has a marked effect on the self-assembly and electronic properties of the parent materials: the optical band gaps and highest occupied molecular orbital levels are affected with the introduction Of fluorine atoms as a result of a combination of inductive effects and rigidification of the main chain. The design of these materials has focused on the self-assembly and solution processability of the materials. All the polymers are readily Soluble in common organic solvents. Self-assembly and planarization of the fluorinated materials in the solid state are identified by a combination of X-ray diffraction studies, absorption spectroscopy, and cyclic voltammetry. The organizational behavior of the films is in contrast to the conformational freedom observed in solution (absorption spectroscopy) and in the gas phase (computational Studies). Thin-film OFETs have been fabricated for the entire polymer series. Hole mobilities have been measured Lip to 10(-3) cm(2)/(V(.)s), with high current modulation (on/off ratios up to 10(5)) and low turn-on voltages (down to 2 V). For the Stille Coupled polymers, replacement of the bridging thiophene unit with selenophene generally increases the hole mobility of the polymers.

KW - thin-film transistors

KW - conjugated polymers

KW - phase-behaviour

KW - solar-cells

KW - semiconductors

KW - derivatives

KW - stacking

KW - devices

KW - sensors

KW - oligothiophene

UR - http://pubs.acs.org/cgi-bin/article.cgi/cmatex/2005/17/i26/pdf/cm051563i.pdf

UR - http://dx.doi.org/10.1021/cm051563i

U2 - 10.1021/cm051563i

DO - 10.1021/cm051563i

M3 - Article

VL - 17

SP - 6567

EP - 6578

JO - Chemistry of Materials

T2 - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 26

ER -